Process Scheme To Improve Divalent Metal Salts Removal From Mono Ethylene Glycol (MEG)

ABSTRACT

A MEG reclamation process includes the step of increasing above 2,000 ppm the divalent metal salts concentration of a rich (wet) MEG feed stream flowing into a precipitator. The increasing step includes routing a salts-saturated MEG slipstream from the flash separator it to the precipitator. The slipstream may be mixed with a fresh water feed stream, a portion of the rich MEG feed stream, or some combination of the two. The rich MEG feed stream also may be split into two streams, with a portion of the stream being heated and routed to the flash separator and the other portion being combined as above with the removed slipstream. The process can be performed on the slipstream after dilution and prior to entering the precipitator or after being loaded into the precipitator. Removal of the insoluble salts may be done in either a batch or continuous mode.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of pending U.S. patentapplication Ser. No. 13/295,666, filed on Nov. 14, 2011, which isincorporated herein by reference.

BACKGROUND

This invention relates to processes designed to treat mono ethyleneglycol (MEG) used in the oil and gas industry, especially in offshorelocations, to control hydrates formation. More particularly, theinvention relates to MEG reclamation processes which are designed toremove salts from a wet MEG feed stream.

In the oil and gas industry, dry (lean) MEG is used to control theformation of hydrates within the produced stream. The now wet (rich) MEGis, in turn, dried by way of a MEG reclamation process so the MEG can beused again in hydrate control. However, the lean MEG cannot be recoveredby simply distilling the rich MEG and water because the rich MEG iscommonly loaded with salts such as calcium chloride and, commonly,lesser amounts of other divalent metal salts like magnesium, barium andstrontium chlorides. The salts have to be removed before the MEG andwater are separated. If the salts are not removed prior to the MEG/waterseparation, the salts accumulate in the process equipment, eventuallyleading to process failure. This is especially problematic in processeswhose design does not include a divalent metal salt removal step.

In processes that do include a divalent metal salt removal step, thedivalent metal is usually removed by reacting it with precipitant agentsuch as sodium carbonate (soda ash), potassium carbonate or sodiumoxalate. The resulting insoluble salt precipitates and is removed assolid crystals. Because the most common divalent metal present in richMEG is calcium and the most common precipitating agent is sodiumcarbonate, the following descriptions are based on calcium removal asrepresentative of divalent metals removal and sodium carbonate asrepresentative of precipitating agents.

In a typical process having a calcium removal step, the calcium in therich MEG will be reacted with sodium carbonate (soda ash) to forminsoluble calcium carbonate and soluble sodium chloride. The insolublecalcium carbonate precipitates and is removed as solid crystals. Thesoluble sodium chloride remains in solution and is separated from therich MEG by flashing the rich MEG under vacuum and at temperature. Thevaporized water and MEG are then separated by partial condensation inwhat is commonly termed a “distillation” tower.

Flashing of the solvents (vaporized water and MEG) for the remainingsalts (mostly sodium chloride) turns the salts into crystals that dropinto a salt-saturated hot MEG solution which, in turn, is used as theheat transfer medium to drive the flashing process. Calcium presence inthis step can promote severe viscosity problems and hinder propersettling of the newly formed crystals.

Calcium removal with soda ash treats the rich MEG stream at about 180°F. and needs about 15 minutes of residence time for the reaction toproceed and form reasonable size calcium carbonate crystals fordecanting and removal. However, experiments conducted by the inventorhave shown that calcium carbonate crystal growth, final size andreaction speed are normally favored by calcium chloride concentrationstypically far above the concentration normally found in the rich MEGstream (usually less than 2,000 ppm). Lower concentrations of calcium inthe precipitator inlet favor small size crystal formation, which in turnincreases the difficulty of removal and residence time for the reactionsto occur. The temperature requirement usually entails the use of heatexchangers to heat up the feed to the reaction temperature and mayrequire more real estate than available, especially in offshorelocations.

A need exists for a MEG reclamation process that removes calcium moreeffectively especially when the initial design did not include a calciumremoval step (which is then found necessary later on) and intensifiesthe calcium removal process to make better use of limited space andexisting equipment. Notwithstanding, the process can also be used fornew designs to provide for a more compact divalent metal removal stepthan the current art.

SUMMARY

A system for removing divalent metals from a mono-ethylene glycol(“MEG”) feed stream includes treating with a precipitating agent a firstMEG stream having a high concentration of divalent metal salts whichexits a flash separator to induce divalent salt separation andprecipitation in a precipitator sized to receive the first high divalentmetal salts concentration MEG feed stream; and means for returning tothe flash separator a second (now) lower divalent salts-saturated MEGstream exiting the precipitator.

A process (either continuous or batch) for removing divalent metal salts(especially calcium) from MEG as insoluble salts includes the steps of

-   -   (i) increasing a divalent metal salts concentration of a MEG        feed flowing into a precipitator so that the resulting divalent        metal salts concentration of the MEG feed is above 2,000 ppm;    -   (ii) treating the resulting divalent metal salts-concentration        MEG feed in the precipitator with a precipitating agent;    -   (iii) removing from the precipitator the insoluble salt formed        and a divalent metal salts-saturated MEG stream;    -   (iv) routing the removed divalent metal salts-saturated MEG        stream into a flash separator.

In a preferred embodiment, the divalent metal is calcium and theincreasing step increases the calcium concentration to about 25,000 ppm.The increasing step may include the sub-steps of removing asalt-saturated MEG slipstream from a liquid inventory of the flashseparator and routing the removed slipstream to the precipitator. Theremoved slipstream may be mixed with a fresh water feed stream, aportion of the rich MEG feed stream, or some combination of the two. Themixed stream is then routed to the precipitator. Because of the way inwhich the process treats the increased calcium rich MEG feed stream, anysodium carbonate added to this stream prior to the precipitator isprevented from entering the flash separator.

The rich MEG feed stream may be split into two streams, with a portionof the stream being heated and routed to the flash separator and theother portion being combined as above with the removed slipstream. Theremoved slipstream may be cooled prior to it entering the precipitator.The fresh water feed stream or rich MEG feed stream (or some combinationof the two) may be used to cool the slipstream.

Removal and processing of the slipstream from the flash separator may bedone in either a batch mode or a continuous mode. When operating in abatch mode, the slipstream can be removed when the calcium concentrationwithin the flash separator reaches a preset value (typically in a rangeof 40,000 to 50,000 ppm). In either mode, the calcium concentrationwithin the separator should be kept below a plugging range (nearing the60,000 ppm zone).

Objects of the invention are to (1) remove divalent metals such ascalcium more effectively in less floor-space/volume when compared tocurrent calcium removal processes without the need for additionalspecialized or new types of process equipment; (2) speed the reaction ofcalcium removal and promote larger-sized crystal formation by increasingthe calcium ion concentration above 2,000 ppm of the feed entering theprecipitator; (3) increase the velocity and conversion rate of thecalcium removal reaction by increasing the feed temperature entering theprecipitator via direct mixing with the fresh feed or water; (4) preventthe release of carbon dioxide by avoiding the introduction of solubleprecipitating agents into the elevated temperature flash separator orseparator; and (5) reduce MEG losses significantly by minimizing the MEGcontent contained in the disposed salts. In the case of calciumcarbonate, direct mixing with fresh feed or water reduces the solubilityof the calcium carbonate and favors higher conversion of calciumchloride into calcium carbonate. Higher conversion is achieved becausethe carbonate precipitates to a greater extent to reach the lowerequilibrium concentration at the higher temperature.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features can be understoodin detail, a more particular description may be had by reference toembodiments, some of which are illustrated in the appended drawings,wherein like reference numerals denote like elements. It is to be noted,however, that the appended drawings illustrate various embodiments andare therefore not to be considered limiting of its scope, and may admitto other equally effective embodiments.

FIG. 1 shows a schematic of a prior art process that considers thepresence of calcium in the feed. The low calcium concentration(typically less than 2,000 ppm) of the wet MEG, fresh feed stream isheated and mixed with sodium carbonate. The mixture enters aprecipitator where the calcium carbonate forms and precipitates. Theprecipitation process removes calcium from the stream and thesalt-saturated MEG stream is further heated and routed to a flash drumor separator. In the flash separator, the water and most of the MEG areflashed off to be distilled downstream. Sodium chloride is removed ascrystals from the bottom of the flash separator.

FIG. 2 shows a schematic of a prior art process that does not properlyconsider the presence of calcium in the rich MEG feed stream. Therefore,calcium in the feed stream accumulates in the flash separator andimpairs sodium chloride removal. Calcium accumulation in the flashseparator may also lead to severe salt deposition and plugging.Operators may be forced to dump MEG from the flash separator and replaceit with fresh MEG to purge calcium or lower its concentration in theflash separator. For an existing facility, it may not be feasible toturn the process shown in FIG. 2 into that of FIG. 1, with afull-fledged precipitator and preheating system. Additionally, the lowcalcium concentration in the rich MEG feed stream may lead to requiringa precipitator much larger in size than current space constraints canaccommodate.

FIG. 3 shows a preferred embodiment of a MEG reclamation processpracticed according to this invention. The process removes calcium froma rich MEG feed stream by using smaller equipment than the process ofFIG. 1 and effectively removes accumulated calcium from the flashseparator.

FIG. 4 presents another preferred embodiment of a MEG reclamationprocess practiced according to this invention in which the same conceptsas those of FIG. 3 are used.

FIG. 5 presents another embodiment of the MEG reclamation processsuitable for operating in a batch mode using the same concepts as thoseof FIGS. 3 and 4.

ELEMENTS AND NUMBERING USED IN THE DRAWINGS AND THE DETAILED DESCRIPTION

10 MEG reclamation process with calcium removal

20 Fresh, wet (rich) MEG feed stream

22 Heating medium

24 Pre-Heated fresh feed stream

26 Precipitator feed stream

28 Precipitating agent

30 Fresh water feed stream

32 Fresh feed/fresh water stream

34 Diluted slipstream

40 Precipitator

42 Calcium carbonate stream

43 Recycle loop

44 Calcium salts-saturated MEG stream

46 Heating medium

48 Heated calcium salts-saturated MEG stream

50 Flash separator stream

60 Flash drum or separator

62 Slipstream

64 Salt crystal outlet stream

66 Vaporized water and MEG stream

68 Heat transfer medium

DETAILED DESCRIPTION

In the following description, numerous details are set forth to providean understanding of some embodiments of the present disclosure. However,it will be understood by those of ordinary skill in the art that thesystem and/or methodology may be practiced without these details andthat numerous variations or modifications from the described embodimentsmay be possible.

Referring first to FIG. 3, a preferred embodiment of a MEG reclamationprocess 10A practiced according to this invention begins with a fresh,wet (rich) MEG feed stream 20 which is then heated by way of a heatingmedium 22 to form a pre-heated fresh feed stream 24. Fresh feed stream20 is typically low in calcium concentration (less than 2,000 ppm). Thepre-heated fresh feed stream 24 is mixed with a slipstream 62 that hasbeen removed from a liquid inventory of a flash drum or separator 60 toform a precipitator feed stream 26. A precipitating agent 28, preferablysodium carbonate, is added to the precipitator feed stream 26.

Mixing slipstream 62 with the pre-heated fresh feed stream 24 increasesthe calcium concentration of the precipitator feed stream 26 above thatof initial fresh feed stream 20 but below that of slipstream 62. Ingeneral terms, the calcium concentration of precipitator feed stream 26is in a range of about 10,000 to 30,000 ppm. However, the exact calciumconcentration of the stream 26 depends upon the flow rate and calciumconcentration of the pre-heated fresh feed stream 24 and the slipstream62 (which may be in a range of about 25,000 to 50,000 ppm). Slipstream62 increases the temperature of the precipitator feed stream 26 becausethe flash separator 60 operates at higher temperature than does theprecipitator 40. This allows the heating medium 22 to be reduced in sizecompared to prior art processes (see e.g. FIG. 1) and yet still meet thedesired temperature for precipitator feed stream 26.

A calcium carbonate stream 42 exits a bottom end of precipitator 40 anda calcium salts-saturated MEG stream 44 exits a top end. The calciumsalts-saturated MEG stream 44 is heated by a flash separator heater 46and the heated calcium salts-saturated MEG stream 48 is routed intoflash separator 60. A salt crystals stream 64 exits a bottom end offlash separator 60 and a vaporized water and MEG stream 66 exits a topend. The water and MEG components of the vaporized water and MEG stream66 are then separated from one another by partial condensation in whatis commonly termed a “distillation” tower (not shown).

To maintain a constant residence time in precipitator 40, a person ofordinary skill in the art would recognize the volume of the precipitator40 must increase linearly with the total flow of precipitator feedstream 26. However, because the precipitation reaction is basically asecond order one in calcium concentration, the effect of the increase inoverall calcium concentration in is the precipitator feed stream 26 (inmost cases) more than offsets the need for increased residence time.Therefore, the same conversion of calcium removal can be reached nowwith less residence time compared to prior art processes.

The size/volume of precipitator 40, the flow rate of the pre-heatedfresh feed stream 24, the recirculation flow rate of the slipstream 62,and the heat exchange of the heated calcium salts-saturated MEG steam 48are preferably designed so that the steady state calcium concentrationin the flash separator 60 is maintained below the severe plugging range(typically in the range of 50,000 to 60,000 ppm). The removal ofslipstream 62 from flash separator 60 may be operated in a batch mode,drawing the slipstream 62 from the flash separator 60 when the overallcalcium concentration within the flash separator 60 reaches a preset butsafe high value.

Referring now to FIG. 4, another preferred embodiment of a MEGreclamation process 10B practiced according to this invention isillustrated. In this embodiment, fresh, wet (rich) MEG feed stream 20 issplit into two fresh feed streams 20A, 20B, with fresh feed stream 20Abeing heated by heating medium 22 to produce a pre-heated fresh feedstream 24 which is combined the salt-saturated MEG stream 44 exitingprecipitator 40 to form flash separator stream 50. Flash separatorstream 50 is then routed to flash separator 60. A calcium carbonatestream 42 exits a bottom end of precipitator 40 and a salt-saturated MEGstream 44 exits a top end.

Fresh feed stream 20B combines with slipstream 62 from the flashseparator 60 to form precipitator feed stream 36. Unlike process 10A ofFIG. 3, in process 10B slipstream 62 is partially diluted (to avoidcrystallization upon cooling and improve heat transfer) with fresh feedstream 20B and fresh water stream 30 to form fresh feed/fresh waterstream 32. The high concentration calcium slipstream 62 is then combinedwith fresh feed/fresh water stream 32 to form a diluted slipstream 34whose temperature is further adjusted by the heat transfer medium 68(cooling or heating depending on the specifics of the design situation)so that the resulting precipitator feed stream 36 is at the requiredprecipitator temperature. The dilution and temperature adjustment ofslipstream 62 could be provided by the fresh feed 20B itself but whetherthis is best or desired in any given application depends upon availableutilities and other practical considerations. The removal of slipstream62 can be operated in batch or continuous mode as previously described.

Referring now to FIG. 5, another preferred embodiment of a MEGreclamation process 10C is illustrated which is very well suited forbatch calcium removal applications, even though it can also operate in acontinuous mode. The batch removal process is described herein.

Fresh feed 20 is heated with a heating medium 22 and the resultingpreheated fresh feed stream 24 is flashed in the flash separator 60. Thesoluble calcium salts accumulate in the flash separator 60 untilreaching a high calcium concentrate trigger point (preferably within arange of 25,000 to 50,000 ppm).

Upon reaching the calcium concentration trigger point, a slip stream 62is taken from the flash separator 60 and preferably mixed with sodiumcarbonate 28 (the precipitating agent) to become the precipitator feedstream 26. The flows are kept until the batch to be treated is loadedinto the precipitator 40 to start the precipitation reaction phase.After the precipitator 40 is loaded, the fluids in the precipitator 40are allowed to react and form the calcium carbonate crystals. The fluidsmay be re-circulated in a recycle loop 43 (as depicted) or otherwisestirred to promote good contact of the calcium chloride and the sodiumcarbonate to form the calcium carbonate crystals. Reaction times willusually be such total batch treatment can be completed with an 8-hourwork shift.

At the completion of the precipitation reaction phase, the solids 42 areremoved from the precipitator 40 and the (now) lower calcium-saltssaturated MEG stream 44 is returned to the flash separator 60. The solidseparation is not limited to decanting because separation can beenhanced by using centrifuges or other types of solid/liquid separators.

While preferred embodiments of a MEG reclamation system and process havebeen described in detail, a person of ordinary skill in the artunderstands that certain changes can be made in the arrangement ofprocess steps and type of components used in the process withoutdeparting from the scope of the following claims.

Although the preceding description has been described herein withreference to particular means, materials and embodiments, it is notintended to be limited to the particulars disclosed herein; rather, itextends to all functionally equivalent structures, methods, and uses,such as are within the scope of the appended claims.

What is claimed is:
 1. A process for removing divalent metals from amono-ethylene glycol (“MEG”) stream, the process comprising: increasinga divalent metal salts concentration of a first MEG stream; wherein theincreasing occurs between a hydrate inhibition use of the first MEGstream and a precipitation reaction of the first MEG stream.
 2. Aprocess according to claim 2 wherein the increasing includes: adding asecond MEG stream to the first MEG stream; the second MEG stream havinga higher divalent metal salts concentration than the first MEG stream.3. A process according to claim 2, the second MEG stream having a lowerwater content than the first MEG stream.
 4. A process according to claim2 wherein the second MEG stream is from a concentrator.
 5. A processaccording to claim 4 further comprising: removing the second MEG streamfrom the concentrator when the divalent metal salts concentration withinthe concentrator reaches a preset value.
 6. A process according to claim4 further comprising: maintaining a divalent metal salts concentrationin the concentrator below a plugging range of the concentrator.
 7. Aprocess according to claim 4 wherein the divalent metal saltsconcentration in the concentrator is in a range of 25,000 to 50,000 ppm.8. A process according to claim 2 further comprising: adjusting atemperature of the second MEG stream.
 9. A process according to claim 2further comprising: adjusting the higher divalent metal saltsconcentration of the second MEG stream.
 10. A process according to claim9 further comprising: the adjusting including mixing the second MEGstream with a water stream.
 11. A process according to claim 9 furthercomprising: the adjusting including mixing the second MEG stream with aportion of the first MEG stream.
 12. A process according to claim 1wherein, after the increasing, the divalent metal salts concentration ofthe first MEG stream is at least 25,000 ppm.
 13. A process for removingdivalent metals from a mono-ethylene glycol (“MEG”) stream, the processcomprising: increasing a divalent metal salts concentration of a firstMEG stream by adding a second MEG stream to the first MEG stream; thesecond MEG stream originating from a concentrator and having a higherdivalent metal salts concentration than the first MEG stream; whereinthe increasing occurs between a hydrate inhibitor use of the first MEGstream and a precipitation reaction of the first MEG stream.
 14. Aprocess according to claim 13 further comprising: removing the removingthe second MEG stream from the concentrator when the divalent metalsalts concentration within the concentrator reaches a preset value. 15.A process according to claim 13 further comprising: adjusting atemperature of the second MEG stream.
 16. A process according to claim13 further comprising: adjusting the higher divalent metal saltsconcentration of the second MEG stream.
 17. A process according to claim13 wherein the concentrator is located downstream of a reactor where theprecipitation reaction of the first MEG stream occurs.
 18. A process forremoving divalent metals from a mono-ethylene glycol (“MEG”) stream, theprocess comprising: increasing a divalent metal salts concentration of afirst MEG stream by adding a second MEG stream to the first MEG stream;the second MEG stream having a higher divalent metal salts concentrationthan the first MEG stream and a lower water content than the first MEGstream; wherein the increasing occurs between a hydrate inhibitor use ofthe first MEG stream and a precipitation reaction of the first MEGstream; and wherein the second MEG stream is removed from a concentratorlocated downstream of the reactor.
 19. A system for removing divalentmetal salts from a mono-ethylene glycol (“MEG”) feed, the systemcomprising: means for increasing a divalent metal salts concentration ofa first MEG stream; and a precipitation reaction of the first MEGstream; the means for increasing being located between a hydrateinhibition use of the first MEG stream and the precipitation reaction ofthe first MEG stream.
 20. A system according to claim 19, the means forincreasing including: a concentrator configured to provide a second MEGstream for addition to the first MEG stream; the second MEG streamhaving a higher divalent metal salts concentration than the first MEGstream.